JP2013522395A - Dewaxing of renewable diesel fuel - Google Patents

Abstract

  The feed containing the hydrotreated biocomponent portion, and optionally the mineral portion, can be processed under contact conditions for isomerization and / or dewaxing. The sulfur content of the raw material for dewaxing can be selected based on the hydrogenated metal used for the catalyst. Diesel fuel products with improved cold flow properties can be produced.

Description

  The present invention relates to hydroprocessing of a fuel feedstock (raw or raw material) derived from a biocomponent source and hydroprocessing of a blend of biocomponent and mineral (mineral or mineral) fuel feedstock.

  Biodiesel is increasingly being recognized as a diesel fuel component. “Biodiesel” typically includes fatty acid esters made from vegetable oil triglycerides, which may include various crops or waste oils, or other animal fats. Algal sources can also produce suitable triglycerides. The raw vegetable oil or animal fat triglyceride is reacted with an alcohol such as methanol to form a fatty acid alkyl ester and specifically achieve a viscosity within the diesel specification. A common type of fatty acid alkyl ester is fatty acid methyl ester, or FAME. A separate ASTM standard (D6751-07) has been issued that covers biodiesel when blended with conventional diesel, but some of the standards do not match the conventional diesel standards required for blended blends . For example, the Biodiesel Cloud Point standard is indicated as “report only” with a footnote that it is usually higher than conventional diesel fuel and that this needs to be taken into account. Biodiesel fuel often has a relatively high cloud point. As a result, blends of biodiesel and conventional diesel can make the entire blend inadequate in terms of cloud point and / or other cold flow characteristics.

  U.S. Patent Nos. 5,099,036 and 5,037,059 each describe a method of hydrotreating diesel range feedstocks based on biocomponent sources, such as plant or animal fat / oil. This hydrotreating method includes a step of subjecting the biocomponent raw material to hydrotreating conditions, followed by a hydrotreating step for isomerizing the raw material. The isomerization catalysts identified in these publications include SAPO-11, SAPO-41, ZSM-22, ZSM-23, and ferrierite. The isomerization catalyst is described to also contain a Group VIII metal such as Pt and a binder such as alumina. The lowest cloud point specified in these references is -14 ° C to -22 ° C. The level of n-paraffin remaining in the isomerized diesel product was not specified.

  Patent Document 3 describes a method for producing diesel fuel from a Tall Oil Fatty Acid (TOF oil fatty acid) (TOFA) fraction. The TOFA fraction is described as containing triglycerides present in the biocomponent feed such as rapeseed oil, sunflower oil, or palm oil. This method involves hydroprocessing followed by isomerization. The most preferred isomerization catalyst is described as a low acid catalyst. SAPO-11 combined with alumina and ZSM-22 or ZSM-23 combined with alumina are provided as examples of isomerization catalysts. Isomerization catalysts are also described as containing supported Group VIII metals such as Pt. No cloud point is provided for diesel fuel products. The lowest reported value for the amount of n-paraffin in the isomerization product is 13%.

  Patent Document 4 describes a hydrogen treatment method of a biocomponent raw material in a single step. This single step performs both hydrodeoxygenation and hydroisomerization. This single-step catalyst is described as containing both a metal component and an acidic component. The metal component is described as platinum or palladium. A wide variety of zeolites have been described for acidic components. A porous solid support may also be present. The lowest cloud point reported for diesel fuel produced according to the process described in this publication is -11 ° C to -16 ° C. Cloud points below −20 ° C. are also reported in the comparative examples. After treatment, the reported diesel product had an n-paraffin content of at least 14.5%.

  Patent Document 5 describes a method of treating a mixture of a vegetable oil and a mineral raw material with a catalyst under hydrotreating conditions. The catalyst can include cobalt and molybdenum supported on a dealuminated form of ZSM-5.

  Patent Document 6 describes a method for treating biocomponent feedstock oil by firstly hydrotreating the feedstock and then dewaxing the feedstock under catalytic dewaxing conditions. The dewaxing catalyst can be a ZSM-48 containing catalyst comprising platinum.

European Patent No. 1741767 European Patent No. 1741768 US Patent Application Publication No. 2007/0006523 US Patent Application Publication No. 2006/0207166 US Patent Application Publication No. 2009/0019763 US Patent Application Publication No. 2008/0125516

  What is needed is a method for producing biocomponent-based diesel fuels with improved properties to facilitate use in commercial fuel supplies. Preferably, the method will allow for the production of diesel fuel that meets any current cold flow property requirements while also providing improved cetane.

  One aspect of the present invention is a step of mixing a biocomponent raw material part with a mineral (mineral or mineral) raw material part to form a mixed raw material oil (raw material or raw material), wherein the mixed raw material oil is less than about 500 wppm sulfur Effective isomerization and / or dewaxing (or dewaxing) conditions comprising a content and a biocomponent feedstock portion of at least about 25% by weight of the mixed feedstock; and a temperature of at least about 350 ° C. A step of contacting the mixed feedstock with an isomerization / dewaxing catalyst, wherein the isomerization / dewaxing catalyst comprises ZSM-48 and at least 0.5 wt% Pt, Pd, or combinations thereof; ZSM-48 produces a isomerized and / or dewaxed product having a silica to alumina ratio of about 75: 1 or less and a isomerization and / or dewaxing condition with a cloud point of about -20 ° C or less. You Includes the step is sufficient for, biocomponent feedstock portions, the mixed feedstock is hydrotreated prior to being contacted with the isomerization / dewaxing catalyst, isomerization of diesel fuel and / or to dewaxing methods.

  Another aspect of the present invention is a process for hydrotreating a feedstock containing at least about 25 wt% biocomponent portion of a feedstock (raw or raw material) under effective hydrotreating conditions, wherein the biocomponent Hydrotreating feedstock under effective isomerization and / or dewaxing conditions comprising a portion having an oxygen content of at least about 8 wt% prior to hydrotreating; and a temperature of at least about 370 ° C; Contacting with an isomerization / dewaxing catalyst, wherein the isomerization / dewaxing catalyst is selected from Beta, USY, ZSM-5, ZSM-35, ZSM-23, ZSM-48, or combinations thereof Clouding point comprising isomerization / dewaxing conditions of about −20 ° C. or less, comprising at least about 2% by weight of hydrogenated metal comprising molecular sieves and a combination of Ni and at least one of W and Mo. Having including an effective process to produce a isomerization and / or dewaxed product, isomerization of diesel fuel and / or to dewaxing methods.

1 depicts a reaction system suitable for carrying out the process according to the invention. Figure 2 shows cloud point data for various ingredients processed under various test conditions.

In some embodiments, the mixture of biocomponent feed and mineral feed can be processed under hydroprocessing conditions to produce a diesel fuel with beneficial cold flow properties. For example, a mixture of at least 5% by weight hydrotreated biocomponent feedstock portion can be combined with a mineral feedstock portion to form a diesel boiling range feedstock. Mixed diesel range feedstocks are isomers that contain Group VIII metals, such as Pt or Ni, and optionally (eg, usually when the Group VIII metal is Ni, etc.) Group VIB metals, such as Mo and / or W. Can be exposed to a crystallization / dewaxing catalyst. Preferably, the base of the isomerization / dewaxing catalyst is a suitable ratio of silicon to aluminum in the zeolite (eg, in the general oxide form, ie silica and alumina, abbreviated as Si / Al ₂ ). And molecular sieves such as zeolites. The mixed diesel range feedstock can be exposed to an isomerization / dewaxing catalyst under effective catalytic isomerization and / or dewaxing conditions. This can result in improved cold flow properties, particularly diesel boiling range products that are at least improved (or higher) cloud point and suitable for use as diesel fuel. Additionally or alternatively, either the mixed feedstock or one or both of the individual feedstock portions can optionally be hydrotreated prior to isomerization / dewaxing. Similarly or alternatively, the feedstock can optionally be hydrofinished after isomerization / dewaxing.

  One potential use of the method according to the invention is to take advantage of “winter diesel” processing capacity during a relatively warm month. Typical diesel fuel may not be suitable for climates that have cryogenic temperatures, such as -20 ° C. or lower in winter. In order to avoid the cold flow problem, diesel fuel with improved cold properties can be produced. One method of producing such “winter diesel” is to isomerize diesel fuel using an isomerization process, such as catalytic dewaxing.

  Refinery utilization can be increased by using isomerization equipment used to produce winter diesel during relatively warm months for additional production of biodiesel. Isomerization can be beneficial for diesel fuels based on biocomponent sources. Diesel fuels based on biocomponent feedstocks may tend to have higher cetane numbers than mineral diesel feedstocks, but the cloud point temperature and other low temperature flow characteristics of biocomponent based diesel fractions typically It is not very preferable. Isomerization of the biocomponent diesel fraction can allow an increase in the cetane number of the biocomponent fraction added to the diesel fuel pool while mitigating any loss of cold flow properties, particularly cloud point.

Feedstock In the following discussion, a “mineral oil” feedstock is a hydrocarbon-based oil from a fossil / mineral fuel (or mineral fuel) source, such as crude oil, such as by CAS No. 8020-83 by Aldrich. It means that it is not a commercially available organic product such as the one sold in -5.

  In the following discussion, biocomponent feedstock means a hydrocarbon feedstock derived from biological feedstock components from biocomponent sources such as plants, animals, fish, and / or algae. Note that for the purposes of this document, vegetable fat / oil generally means any plant-based material and may include fat / oil derived from sources such as plants of the genus Jatropha. . In general, biocomponent sources can include vegetable fat / oil, animal fat / oil, fish oil, pyrolysis oil, and algal lipid / oil, and components of such materials, in some embodiments One or more types of lipid compounds can be specifically mentioned. Lipid compounds are typically biological compounds that are insoluble in water but soluble in non-polar (or fatty) solvents. Non-limiting examples of such solvents include alcohol, ether, chloroform, alkyl acetate, benzene, and combinations thereof.

  Major classes of lipids include fatty acids, glycerol-derived lipids (including fats, oils and phospholipids), sphingosine-derived lipids (including ceramides, cerebrosides, gangliosides, and sphingomyelin), steroids and their derivatives, terpenes and their Derivatives, fat-soluble vitamins, certain aromatic compounds, and long chain alcohols and waxes are included, but are not necessarily limited thereto.

  In living organisms, lipids generally serve as cell membrane platforms and as fuel storage forms. Lipids can also be found conjugated to proteins or carbohydrates, such as in the form of lipoproteins and lipopolysaccharides.

  Examples of vegetable oils that can be used according to the present invention include rapeseed (canola) oil, soybean oil, coconut oil, sunflower oil, palm oil, palm kernel oil, peanut oil, linseed oil, tall oil, corn oil, castor oil , Jatropha oil, jojoba oil, olive oil, flux seed oil, camelina oil, safflower oil, babas oil, beef tallow oil and rice bran oil, but are not limited thereto.

Vegetable oils as mentioned herein can also include processed vegetable oil materials. Non-limiting examples of processed vegetable oil materials include fatty acids and fatty acid alkyl esters. The alkyl esters, typically include _C 1 -C ₅ alkyl ester. One or more of the methyl, ethyl, and propyl esters are preferred.

  Examples of animal fats that can be used according to the present invention include, but are not limited to, beef tallow, lard, turkey fat, fish fat / oil, and chicken fat. Animal fats can be obtained from any suitable source including restaurants and meat production facilities.

Animal fat as referred to herein also includes processed animal fat materials. Non-limiting examples of processed animal fat materials include fatty acids and fatty acid alkyl esters. The alkyl esters, typically include _C 1 -C ₅ alkyl ester. One or more of the methyl, ethyl, and propyl esters are preferred.

  Algal oils or lipids are typically contained in algae in the form of membrane components, storage products, and metabolites. Certain algal strains, especially microalgae such as diatoms and cyanobacteria, contain proportionally high levels of lipids. The algal source for the algal oil can contain varying amounts of lipids, for example 2% to 40% by weight, based on the total weight of the biomass itself.

  Algal sources for algal oil include, but are not limited to, unicellular and multicellular algae. Examples of such algae include red algae (rhodophyte), green algae (chlorophyte), heterocontophyte algae (tribophyte), gray algae (glaucophyte), chlorarachniophyte, Examples include haptophyte, cryptomonad, dinoflagellum, phytoplankton, and combinations thereof. In one embodiment, the algae can be of the class Chlorophyceae and / or Haptophyta. Specific species include Neochloris oleoabundans, Scenedesmus dimorphhus, Euglena gracilis, and euglena calcipres. Examples include, but are not limited to, Prinnesium parvum, Tetraselmis chui, and Chlamydomonas reinhardtii.

Examples of biocomponent raw materials that can be used in the present invention include any of those mainly containing triglycerides and free fatty acids (FFA). Triglycerides and FFAs typically contain aliphatic hydrocarbon chains in their structure having 8 to 36 carbons, preferably 10 to 26 carbons, such as 14 to 22 carbons. The type of triglyceride can be determined by their fatty acid constituents. Fatty acid constituents can be easily measured using gas chromatography (GC) analysis. This analysis includes the steps of extracting fat or oil, saponifying the fat or oil (hydrolyzing), preparing an alkyl (eg methyl) ester of the saponified fat or oil, and GC analysis And measuring the type of (methyl) ester using. In one embodiment, based on the total triglycerides present in the lipid material, the majority (ie, greater than 50%) of the triglycerides present in the lipid material can consist of C ₁₀ -C ₂₆ fatty acid components. . In addition, triglycerides are molecules that have substantially the same structure as the reaction product of glycerol and three fatty acids. Thus, although triglycerides are described herein as consisting of fatty acids, it should be understood that the fatty acid component does not necessarily contain hydrogen carboxylates. In one embodiment, based on the total triglyceride content, the majority of the triglycerides present in the biocomponent feed may preferably consist of C ₁₂ -C ₁₈ fatty acid components. Other types of raw materials derived from biological raw material components can include fatty acid esters, such as fatty acid alkyl esters (eg, FAME and / or FAEE).

  Biocomponent-based diesel boiling range feed streams typically have relatively low nitrogen and sulfur content. For example, a biocomponent based feed stream can contain up to about 500 wppm nitrogen, such as up to about 300 wppm nitrogen or up to about 100 wppm nitrogen. Instead of nitrogen and / or sulfur, the main heteroatom component in the biocomponent feed is oxygen. The biocomponent diesel boiling range feed stream can include, for example, about 10 wt% or less oxygen, about 12 wt% or less oxygen, or about 14 wt% or less oxygen. A suitable biocomponent diesel boiling range feed stream may contain at least about 5 wt% oxygen, such as at least about 8 wt% oxygen, prior to hydroprocessing. The biocomponent feed stream can include an olefin content of at least about 3 wt%, such as at least about 5 wt% or at least about 10 wt%, prior to hydroprocessing.

  In certain embodiments, the feedstock can include up to about 100% feedstock having a biocomponent origin. This can be a hydrotreated vegetable oil feedstock, a hydrotreated fatty acid alkyl ester feedstock, or another type of hydrotreated biocomponent feedstock. The hydrotreated biocomponent feed is at least partially (meaning only at least 50%, preferably significantly, at least 90%, preferably at least 95%, such as at least 98%, at least 99%, at least 99% Means 9.9%, at least 99.97%, at least 99.98%, or at least 99.99%, etc., more preferably substantially close enough to be reasonable under those circumstances A) a raw material that has been previously hydrotreated to deoxygenate the raw material. In another embodiment, the non-hydrotreated biocomponent feed can be hydrotreated to substantially deoxygenate the feed prior to other hydrotreating. The portion of the feedstock having a biocomponent origin can be at least about 5% by weight, such as at least about 25% by weight, at least about 50% by weight, or at least about 75% by weight.

  Mineral hydrocarbon feedstock (or feedstock) means hydrocarbon feedstock derived from the crude oil provided, but optionally, preferably to one or more separation and / or other refining processes. Preferably, the mineral hydrocarbon feedstock is or comprises a petroleum feedstock that boils above the diesel range. Examples of suitable feedstocks include, but are not limited to, virgin distillates, kerosene, diesel boiling range feedstocks, jet fuels, light cycle oils, and combinations thereof, including their hydroprocessed versions. .

  The mineral feed stream for blending with the biocomponent feed stream can have a nitrogen content of about 50 wppm to about 2000 wppm, preferably about 50 wppm to about 1500 wppm, such as about 75 wppm to about 1000 wppm. Additionally or alternatively, a feed stream suitable for use herein can have a sulfur content of from about 100 wppm to about 10,000 wppm, such as from about 200 wppm to about 5000 wppm or from about 350 wppm to about 2500 wppm. Additionally or alternatively, the mixed biocomponent and mineral source have a sulfur content of at least about 5 wppm, such as at least about 10 wppm, at least about 25 wppm, at least about 100 wppm, at least about 300 wppm, at least about 500 wppm, or at least about 1000 wppm. Can do. Independently and / or in this further embodiment, the mixed feedstock (or feedstock) has a sulfur content of about 2000 wppm or less, such as about 1000 wppm or less, about 500 wppm or less, about 300 wppm or less, about 100 wppm or less, or about 50 wppm or less. Can have. Still further or alternatively, the nitrogen content of the mixed feedstock can be about 1000 wppm or less, such as about 500 wppm or less, about 300 wppm or less, about 100 wppm or less, about 50 wppm or less, about 30 wppm or less, or about 10 wppm or less. .

In some embodiments, an isomerization / dewaxing catalyst that includes a sulfide form of a metal, such as an isomerization / dewaxing catalyst that includes nickel and tungsten, can be used. In such embodiments, it may be beneficial for the combined mineral and biocomponent feeds to have at least a minimum sulfur content. The minimum sulfur content can be sufficient to maintain the sulfidation state of the metal sulfide of the isomerization / dewaxing catalyst. For example, the combined mineral and biocomponent feedstock can have a sulfur content of at least about 50 wppm, such as at least about 100 wppm, at least about 150 wppm, or at least about 200 wppm. Additionally or alternatively, the combined mineral and biocomponent feedstock (or feedstock) can have a sulfur content of about 500 wppm or less, such as about 400 wppm or less, or about 300 wppm or less. In any of these embodiments, the additional sulfur to maintain the metal of the isomerization / dewaxing catalyst in the sulfided state is provided by gas phase and / or liquid phase sulfur, such as gas phase H ₂ S. Can do. One potential source of H ₂ S gas can come from hydroprocessing of the mineral portion of the feedstock. If the mineral raw material portion is hydrotreated prior to combination with the biocomponent raw material, at least a portion of the gas phase effluent from the hydroprocessing process / stage, particularly containing sufficient H ₂ S gas, Can be transferred (or sent) with the liquefaction liquid effluent.

  In embodiments where the isomerization / dewaxing stage contains a catalyst that does not include a sulfurized form (eg, including a metal or metal state or oxide state), the additional benefits are a relatively low sulfur content and a relatively low This can be achieved by selecting a raw material with a nitrogen content. In such embodiments, the sulfur content of the feed to the dewaxing stage can advantageously be less than 10 wppm, preferably less than 5 wppm, such as less than 3 wppm. Additionally or alternatively, in such embodiments, the nitrogen content of the feed to the isomerization / dewaxing stage can be advantageously less than 10 wppm, preferably less than 5 wppm, such as less than 3 wppm.

  The content of sulfur, nitrogen, oxygen, and olefins in the feedstock produced by blending two or more feedstocks can typically be determined using a weighted average based on the blended feedstock. . For example, the mineral raw material and the biocomponent raw material can be blended in a ratio of 80 wt% mineral raw material and 20 wt% biocomponent raw material. If the mineral feed has a sulfur content of about 1000 wppm and the biocomponent feed has a sulfur content of about 10 wppm, the resulting blend feed could be expected to have a sulfur content of about 802 wppm.

  Diesel boiling range feed streams suitable for use in the present invention tend to boil within the range of about 215 ° F. (about 102 ° C.) to about 800 ° F. (about 427 ° C.). Preferably, the diesel boiling range feed stream is at least about 215 ° F (about 102 ° C), such as at least about 250 ° F (about 121 ° C), at least about 275 ° F (about 135 ° C), at least about 300 ° F ( About 149 ° C), at least about 325 ° F (about 163 ° C), at least about 350 ° F (about 177 ° C), at least about 400 ° F (about 204 ° C), or at least about 451 ° F (about 233 ° C). Has an initial boiling point. Preferably, the diesel boiling range feed stream has a final boiling point of about 800 ° F (about 427 ° C) or less, or about 775 ° F (about 413 ° C) or less, or about 750 ° F (about 399 ° C) or less. In some embodiments, the diesel boiling range feed stream has a boiling range of about 451 ° F. (about 233 ° C.) to about 800 ° C. (about 427 ° C.). Additionally or alternatively, the feedstock can be characterized by the boiling point required to boil a specified percentage of the feedstock. For example, the temperature required to boil at least 5% by weight of the raw material is referred to as the “T5” boiling point.

  In one embodiment, the mineral feedstock has a T5 boiling point of at least about 230 ° F. (about 110 ° C.), such as at least about 250 ° F. (about 121 ° C.) or at least about 275 ° F. (about 135 ° C.). it can. Additionally or alternatively, the mineral hydrocarbon feedstock has a T95 boiling point of about 775 ° F (about 418 ° C) or less, such as about 750 ° F (about 399 ° C) or less, or about 725 ° F (about 385 ° C) or less. be able to. In another embodiment, the diesel boiling range feed stream also includes kerosene range compounds to provide a feed stream in the boiling range of about 250 ° F. (about 121 ° C.) to about 800 ° F. (about 427 ° C.). be able to.

Hydroprocessing-Isomerization / Dewaxing Catalytic dewaxing involves the removal and / or isomerization of long chain paraffinic molecules from the feedstock. Catalytic dewaxing can be accomplished by selective hydrocracking of these long chain molecules or by hydroisomerization. Hydroisomerization / hydrodewaxing catalysts include molecular sieves such as crystalline aluminosilicate (zeolite) and / or silicoaluminophosphate (SAPO). In certain embodiments, the molecular sieve can be a 1-D or 3-D molecular sieve. In another embodiment, the molecular sieve can be a 10-membered ring 1-D molecular sieve (eg, ZSM-48). Examples of molecular sieves can include, but are not limited to, ZSM-48, ZSM-23, ZSM-35, Beta, USY, ZSM-5, and combinations thereof. In some embodiments, the molecular sieve can comprise or can be ZSM-48, ZSM-23, or a combination thereof. The isomerization / dewaxing catalyst can optionally include a binder, such as alumina, titania, silica, silica-alumina, zirconia, or combinations thereof. In certain embodiments, the binder can include or be alumina, titania, or a combination thereof. In another embodiment, the binder can include or be titania, silica, zirconia, or a combination thereof.

  One characteristic of a molecular sieve that can affect the activity of the molecular sieve is the ratio of silicon to aluminum in the molecular sieve (commonly expressed in oxide form such as silica and alumina). For example, the molecular sieve advantageously has a silica to alumina ratio of about 200 to 1 or less, preferably about 120 to 1 or less, such as about 100 to 1 or less, about 90 to 1 or less, or about 75 to 1 or less. Can have. Additionally or alternatively, the molecular sieve can advantageously have a silica to alumina ratio of at least about 30 to 1, such as at least about 50 to 1, or at least about 65 to 1.

  The isomerization / dewaxing catalyst can also include a metal hydrogenation component, such as a Group VIII metal. Suitable Group VIII metals can include, but are not limited to, Pt, Pd, Ni, and combinations thereof. The isomerization / dewaxing catalyst is advantageously at least about 0.1 wt%, such as at least about 0.3 wt%, at least about 0.5 wt%, at least about 1.0 wt%, at least about 2.0 wt%. %, At least about 2.5 wt%, at least about 3.0 wt%, or at least about 5.0 wt% Group VIII metal. Additionally or alternatively, the isomerization / dewaxing catalyst is about 10.0 wt% or less, such as about 7.0 wt% or less, about 5.0 wt% or less, about 3.0 wt% or less, about 2.5 wt%. % Or less, about 2.0% or less, or about 1.5% or less by weight of Group VIII metal.

  In some embodiments, particularly when the Group VIII metal is a non-noble metal such as Ni, the isomerization / dewaxing catalyst may further comprise a Group VIB metal, such as W and / or Mo. For example, in one embodiment, the isomerization / dewaxing catalyst can include Ni and W, Ni and Mo, or a combination of Ni, Mo, and W. In certain such embodiments, the isomerization / dewaxing catalyst is at least about 0.5 wt%, such as at least about 1.0 wt%, at least about 2.0 wt%, at least about 2.5 wt%. %, At least about 3.0 wt%, at least about 4.0 wt%, or at least about 5.0 wt% Group VIB metal. Additionally or alternatively, the isomerization / dewaxing catalyst is about 20.0 wt% or less, such as about 15.0 wt% or less, about 12.0 wt% or less, about 10.0 wt% or less, about 8.0 wt%. % Or less, about 5.0% or less, about 3.0% or less, or about 1.0% or less by weight of Group VIB metal. In one particular embodiment, the isomerization / dewaxing catalyst can comprise only a Group VIII metal selected from Pt, Pd, and combinations thereof.

Catalytic dewaxing is performed by subjecting the feedstock to a dewaxing catalyst (which may also have and usually have isomerization activity) under effective (catalytic) dewaxing (and / or isomerization) conditions. Can do. Effective dewaxing (and / or isomerization) conditions include at least about 500 ° F. (about 260 ° C.), such as at least about 550 ° F. (about 288 ° C.), at least about 600 ° F. (about 316 ° C.), or A temperature of at least about 650 ° F. (about 343 ° C.) can be mentioned, but is not limited thereto. Additionally or alternatively, the temperature can be about 750 ° F. (about 399 ° C.) or less, such as about 700 ° F. (about 371 ° C.) or less, or about 650 ° F. (about 343 ° C.) or less. Effective dewaxing (and / or isomerization) conditions may additionally or alternatively be at least about 400 psig (about 2.8 MPag), such as at least about 500 psig (about 3.4 MPag), at least about 750 psig (about 5.2 MPag), or A total pressure of at least about 1000 psig (about 6.9 MPag) can be mentioned, but is not limited thereto. Additionally or alternatively, the total pressure is no more than about 1500 psig (about 10.3 MPag), such as no more than about 1200 psig (about 8.2 MPag), no more than about 1000 psig (about 6.9 MPag), or no more than about 800 psig (about 5.5 MPag). Can be. Effective dewaxing (and / or isomerization) conditions may additionally or alternatively be at least about 0.5 hr ⁻¹ , such as at least about 1.0 hr ⁻¹ , at least about 1.5 hr ⁻¹ , or at least about 2.0 hr ^{−. One} liquid space velocity (LHSV) can be mentioned, but is not limited thereto. Additionally or alternatively, LHSV is about 10 hr ^-1 or less, it is possible for example to about 5.0hr ^-1 or less, about 3.0 hr ^-1 or less, or about 2.0 hr ^-1 or less. Effective dewaxing (and / or isomerization) conditions may additionally or alternatively be at least about 500 scf / bbl (about 84 Nm ³ / m ³ ), such as at least about 750 scf / bbl (about 130 Nm ³ / m ³ ) or at least about 1000 scf. A processing gas ratio of / bbl (about 170 Nm ³ / m ³ ) can be mentioned, but is not limited thereto. Additionally or alternatively, the process gas ratio is about 3000 scf / bbl (about 510 Nm ³ / m ³ ) or less, such as about 2000 scf / bbl (about 340 Nm ³ / m ³ ) or less, about 1500 scf / bbl (about 250 Nm ³ / m ³ ). Or about 1250 scf / bbl (about 210 Nm ³ / m ³ ) or less.

  The catalytic dewaxing process can modify the feedstock in several ways. The catalytic dewaxing process can remove oxygen in the biocomponent portion of the feedstock. The olefin in the feed can also be at least partially saturated. The dewaxing process can also improve one or more cold flow properties of the feed, such as pour point and cloud point. Optionally, some sulfur and / or nitrogen removal may also occur. It is pointed out that pre-hydrogenation of the biocomponent feed can substantially remove oxygen and saturate the olefin. As a result, isomerization / dewaxing processes performed on previously hydrotreated feeds may only result in limited additional deoxygenation and / or olefin saturation.

  A typical mineral distillate feed suitable for conversion to a diesel fuel product can have an initial cloud point in the range of about -20 ° C to about 5 ° C. The initial cloud point of the biocomponent raw material can be even higher, including raw materials with an initial cloud point of about 20 ° C. or less. To form a suitable diesel fuel product, the catalytic dewaxing (and / or isomerization) conditions are at least about 10 ° C, such as at least about 20 ° C, at least about 30 ° C, at least about 40 ° C, Or it can be selected to lower the cloud point by at least about 50 ° C.

Hydrotreating-hydrotreating and hydrofinishing In some embodiments, additional hydrotreating can be performed before or after catalytic dewaxing. Prior to isomerization / dewaxing, the feedstock can sometimes be hydrotreated. The hydrotreatment process can remove heteroatoms such as oxygen, sulfur, and nitrogen from the feedstock. The hydroprocessing process can also saturate the olefin.

  The hydroprocessing process can be used with mineral raw materials, biocomponent raw materials, or mixed raw materials. In some embodiments, the mineral portion of the feedstock can be hydrotreated separately from the biocomponent portion of the feedstock. Alternatively, the mineral portion and the biocomponent portion can be combined for hydroprocessing. Yet another option is to hydrotreat a portion of the feed in one or more hydrotreating stages, mix the hydrotreated or partially hydrotreated feed with the second portion, and then It may be that the mixed raw material is hydrotreated. In some embodiments, the biocomponent feedstock portion can be hydrotreated prior to introduction into the reaction system for isomerization / dewaxing according to the present invention. Alternatively, the biocomponent feed portion can be subjected to both hydroprocessing and isomerization / dewaxing steps in a single reaction system.

The hydrotreating catalyst can optionally contain at least one of Group VIB and / or Group VIII metals on a support such as alumina or silica. Examples include, but are not limited to NiMo, CoMo, and NiW supported catalysts. Hydroprocessing conditions can be selected to resemble the isomerization / dewaxing conditions described above. Alternatively, the hydrotreating conditions include temperatures from about 315 ° C. ~ about 425 ° C., about 300 psig (about 2.1MPag) ~ about total pressure 3000 psig (about 21MPag), about 0.2 hr ^-1 ~ about 10 hr ^-1 A hydrogen treatment gas ratio of LHSV, about 500 scf / bbl (about 84 Nm ³ / m ³ ) to about 10,000 scf / bbl (about 1700 Nm ³ / m ³ ) can be mentioned, but is not necessarily limited thereto.

  During the hydrotreatment, the sulfur and nitrogen content of the feedstock can be advantageously reduced. In certain embodiments, the hydroprocessing stage preferably has a sulfur content of less than about 100 wppm, such as less than about 50 wppm, less than about 30 wppm, less than about 25 wppm, less than about 20 wppm, less than about 15 wppm, or less than about 10 wppm. Can be reduced to a suitable level. In another embodiment, the hydrotreating stage can reduce the sulfur content of the feed to less than about 5 wppm, such as less than about 3 wppm. With respect to nitrogen, the hydrotreating step preferably reduces the nitrogen content of the feed to about 30 wppm or less, about 25 wppm or less, about 20 wppm or less, about 15 wppm or less, about 10 wppm or less, about 5 wppm or less, or about 3 wppm or less. Can do. If the hydroprocessing process is performed prior to catalytic isomerization / dewaxing, some or all of the above deoxygenation (and optionally but preferably olefin saturation) is performed during the hydroprocessing process. be able to.

  Hydroprocessing can also be used to deoxygenate biocomponent feedstocks or other oxygen-containing feedstocks. Deoxygenation of the feed can avoid problems associated with catalyst poisoning during hydroprocessing or deactivation due to the formation of water or carbon oxides. The catalytic isomerization / dewaxing process can be used to substantially deoxygenate the feedstock. This is at least 90% of the oxygen present in the biocomponent feedstock, such as at least 95%, at least 98%, at least 99%, at least 99.5%, at least 99.9%, or completely (to a measurable extent) Equivalent to removing everything. Alternatively, the substantial deoxygenation of the feedstock can be achieved by reducing the overall feedstock oxygenate level to 0.1% by weight or less, for example 0.05% by weight or less, 0.03% by weight or less, 0.02% by weight or less. , 0.01% by weight or less, 0.005% by weight or less, 0.003% by weight or less, 0.002% by weight or less, or 0.001% by weight or less.

If a hydroprocessing stage is used prior to isomerization / dewaxing, a separation device can be used to separate impurities before passing the hydroprocessing feedstock through the isomerization / dewaxing stage. The separation device can be a separator, stripper, fractionation device, or another device suitable for separating a gas phase product from a liquid phase product. For example, the separator stage can be used to remove at least a portion of any H ₂ S and / or NH ₃ formed during the hydroprocessing, as desired, eg, formed during the hydroprocessing. The remainder of H ₂ S and / or NH ₃ is transferred to the isomerization / dewaxing stage. Alternatively, the entire effluent from the hydroprocessing stage can be transferred to the isomerization / dewaxing stage as needed. H ₂ S retains its isomerization / dewaxing or other catalytic activity, for example, when provided to an isomerization / dewaxing stage using a catalyst comprising both a Group VIII and a Group VIB hydrogenated metal It should be pointed out that it is believed to facilitate the maintenance of the sulfidation of the hydrogenated metal.

After isomerization / dewaxing, the isomerization / dewaxing feedstock can be hydrofinished. The hydrofinishing stage can be similar to the hydroprocessing stage. For example, hydrofinishing can be a mild hydrotreatment for saturation of any residual olefins and / or residual aromatics. Hydrofinishing after isomerization / dewaxing can be carried out in conjunction with an isomerization / dewaxing step. The hydrofinishing stage can operate at a temperature of about 150 ° C to about 350 ° C, such as about 180 ° C to about 250 ° C. The total pressure in the hydrofinishing stage can be from about 400 psig (about 2.9 MPag) to about 3000 psig (about 20.8 MPag). Liquid hourly space velocity in the hydrofinishing step can be from about 0.1 hr ^-1 ~ about ^{5 hr -1,} such as from about 0.5 hr ^-1 ~ about ^{3 hr -1.} The hydrotreating gas ratio in the hydrofinishing stage can be about 250 scf / bbl (about 42 Nm ³ / m ³ ) to about 10,000 scf / bbl (about 1700 Nm ³ / m ³ ).

  Suitable catalysts for hydrofinishing include hydroprocessing catalysts. Alternatively, hydrofinishing or aromatic saturated catalysts such as Group VIII and / or Group VIB metals supported on a bound support from the M41S family, such as bound MCM-41, can be used. Suitable binders for supports from the M41S family, such as MCM-41, include alumina, silica, or any other binder or combination of binders that can provide a relatively high productivity and / or relatively low density catalyst. Can be mentioned. An example of a suitable aromatic saturation catalyst is alumina bonded mesoporous MCM-41 modified with Pt and / or another metal. Such a catalyst can be modified (impregnated) with a hydrogenated metal such as Pt, Pd, another Group VIII metal, a Group VIB metal, or a mixture of such metals. In some embodiments, the amount of hydrogenated (eg, Group VIII) metal is at least 0.1 wt%, such as at least 0.5 wt% or at least 0.6 wt%, based on the total catalyst weight. Can do. In such embodiments, the amount of hydrogenated metal can be 1.0 wt% or less, such as 0.9 wt% or less, 0.75 wt% or less, or 0.6 wt% or less. Additionally or alternatively, the amount of hydrogenated metal, either individually or in a mixture, is at least 0.1 wt%, such as at least 0.25 wt%, at least 0.5 wt%, at least 0.6 wt% , At least 0.75 wt%, or at least 1 wt%. Additionally or alternatively, in these embodiments, the amount of hydrogenated metal, either individually or in a mixture, is 35% or less, such as 20% or less, 15% or less, 10% or less, or It can be up to 5% by weight.

  In some embodiments, the hydrofinishing step can be performed in the same reactor as the isomerization / dewaxing, for example, at the same process gas flow rate and (approximately the same) contact temperature. Additionally or alternatively, in some embodiments, stripping does not occur between the hydrofinishing stage and the catalytic isomerization / dewaxing stage.

Diesel Product Properties Diesel fuel produced by the above process can have improved properties compared to diesel fuel produced by other isomerization / dewaxing processes. The diesel fuel product can have a cetane number (ASTM D976) of at least about 50, such as at least about 55, at least about 60, or at least about 65. Additionally or alternatively, the diesel fuel product can have a cetane index (ASTM D4737) of at least about 50, such as at least about 55, at least about 60, or at least about 65. Additionally or alternatively, the diesel fuel product can have an n-paraffin content of less than about 10 wt%, such as less than about 8 wt%, less than about 6.5 wt%, or less than about 5 wt%. Additionally or alternatively, the cloud point of the diesel fuel product can be about −30 ° C. or lower, such as about −35 ° C. or lower, or about −40 ° C. or lower.

Additional Embodiments Embodiment 1
Mixing the biocomponent raw material portion with the mineral raw material portion to form a mixed feedstock, wherein the mixed feedstock has a sulfur content of less than about 500 wppm, and the biocomponent feedstock portion is at least about 25 of the mixed feedstock And a step of contacting the mixed feedstock with an isomerization / dewaxing catalyst under effective isomerization and / or dewaxing conditions comprising a temperature of at least about 350 ° C. comprising the steps of: The dewaxing catalyst comprises ZSM-48 and at least 0.5 wt% Pt, Pd, or combinations thereof, wherein ZSM-48 has a silica to alumina ratio of about 75: 1 or less, isomerization and / or Or a process wherein the dewaxing conditions are sufficient to produce an isomerization and / or dewaxing product having a cloud point below about −20 ° C., wherein the biocomponent feedstock isomerizes / mixes the feedstock Hydrotreated prior to being contacted with the wax catalyst, isomerization and / or dewaxing method of diesel fuel.

Embodiment 2
Hydrotreating a feedstock comprising at least about 25 wt% biocomponent portion of the feedstock under effective hydrotreating conditions, wherein the biocomponent portion is at least about 8 wt% prior to hydrotreatment Contacting the hydrotreated feedstock with an isomerization / dewaxing catalyst under effective isomerization and / or dewaxing conditions comprising a temperature of at least about 370 ° C. The isomerization / dewaxing catalyst comprises a molecular sieve selected from Beta, USY, ZSM-5, ZSM-35, ZSM-23, ZSM-48, or combinations thereof, and at least Ni and W and Mo Isomerization and / or derosion comprising at least about 2% by weight of hydrogenated metal in combination with one and the isomerization / dewaxing conditions have a cloud point of about −20 ° C. or less. Containing an effective process to produce a product, isomerization and / or dewaxing method of diesel fuel.

Embodiment 3
The method of embodiment 2, wherein the molecular sieve is ZSM-23 or ZSM-48 having a silica to alumina ratio of about 90: 1 or less.

Embodiment 4
The method of Embodiment 2 or Embodiment 3, wherein the dewaxing catalyst comprises at least about 2 wt% Ni and at least about 10 wt% M, Mo, or combinations thereof.

Embodiment 5
Combining the hydrotreated feedstock with the second feedstock prior to the contacting step with the isomerization / dewaxing catalyst, wherein the mixed feedstock has a sulfur content of about 100 wppm sulfur to about 500 wppm sulfur. The method of any of embodiments 2-4, further comprising:

Embodiment 6
Embodiment 1. The embodiment of Embodiment 1 wherein the mineral feedstock portion is hydrotreated by contacting it with a hydrotreating catalyst comprising at least one hydrogenated metal under effective hydrotreating conditions prior to mixing with the biocomponent feedstock portion. Method.

Embodiment 7
Embodiment 7. The method of embodiment 1 or embodiment 6, wherein the mineral raw material portion is mixed with the biocomponent raw material portion prior to hydrotreating the biocomponent raw material portion.

Embodiment 8
The method of any of embodiments 2-5, wherein the second feedstock comprises a mineral feedstock portion that is hydrotreated under effective hydrotreating conditions prior to mixing with the biocomponent feedstock.

Embodiment 9
The method of any of embodiments 1-8, wherein the isomerization and / or dewaxing product is hydrofinished under effective hydrofinishing conditions.

Embodiment 10
Effective hydroprocessing and / or hydrofinishing conditions include a temperature of about 315 ° C. to about 425 ° C., a total pressure of about 300 psig (about 2.1 MPag) to about 3000 psig (about 21 MPag), about 0.2 hr ^−1. Any of Embodiments 2-9, including an LHSV of about 10 hr ⁻¹ and a hydroprocessing gas ratio of about 500 scf / bbl (about 84 Nm ³ / m ³ ) to about 10,000 scf / bbl (about 1700 Nm ³ / m ³ ) That way.

Embodiment 11
The step of hydrotreating the feedstock produces a hydrotreating feedstock and a gas phase effluent containing H ₂ S, and contacting the hydrotreating feedstock with the isomerization / dewaxing catalyst, The method of any of embodiments 2-10, further comprising contacting at least a portion of the gas phase effluent with an isomerization / dewaxing catalyst.

Embodiment 12
Embodiment 12. The method of any of embodiments 1-11, wherein the biocomponent ingredient portion includes fat and / or oil originating from at least one of plants, animals, fish, and algae.

Embodiment 13
Effective catalytic isomerization / dewaxing conditions include about 400 psig (about 2.8 MPag) to about 1500 psig (about 10.3 MPag) total pressure, about 0.5 hr ⁻¹ to about 5.0 hr ⁻¹ LHSV, and The method of any of embodiments 1-12, wherein a process gas ratio of from about 500 scf / bbl (about 84 Nm ³ / m ³ ) to about 2000 scf / bbl (about 340 Nm ³ / m ³ ) is mentioned.

Embodiment 14
The method of any of embodiments 1-13, wherein the hydrotreating feed stream is transferred (or sent) to the isomerization / dewaxing step without intermediate separation.

Embodiment 15
(I) the mixed feedstock has a sulfur content of about 50 wppm or less and a nitrogen content of about 20 wppm or less; (ii) the hydrotreated feedstock has a sulfur content of about 100 wppm sulfur to about 500 wppm sulfur; Or (iii) The method of any of embodiments 1-14, which is both (i) and (ii).

Reaction System Example A reaction system suitable for carrying out the above process is shown schematically in FIG. In FIG. 1, the mineral hydrocarbon feedstock 110 can be introduced into the first hydrotreating reactor 120. A hydroprocessing gas stream 115 can also be introduced into the hydroprocessing reactor 120. The mineral hydrocarbon feedstock can be subjected to hydroprocessing conditions in the first hydroprocessing reactor 120 in the presence of one or more catalyst beds containing a hydroprocessing catalyst. Preferably, the hydrotreating can reduce the sulfur content of the treated feedstock to about 50 wppm or less, such as about 10 wppm or less, about 5 wppm or less, or about 3 wppm or less. Additionally or alternatively, the hydrotreating can preferably reduce the nitrogen content of the treated feedstock to about 10 wppm or less, such as about 5 wppm or less, or about 3 wppm or less. Hydrotreating feedstock 118 optionally flows from hydrotreating reactor 110 to separator 125, where the vapor phase product can be separated from the liquid phase product. The liquid output 128 from the separator 125 can then be combined with the biocomponent feedstock 112.

  In an alternative embodiment, the hydroprocessing reactor 120 and the separation device 125 can be omitted. In such embodiments, the mineral hydrocarbon feed 110 can be passed directly to the conduit 128 for combination with the biocomponent feed 112. Similarly, in such embodiments, preferably both the mineral feed 110 and the biocomponent feed 112 can be hydrotreated in advance. In another alternative embodiment, the biocomponent feedstock 112 can be introduced into the hydroprocessing reactor 120. In such embodiments, (a) the biocomponent feed can be mixed with the mineral feed prior to entering the hydrotreating reactor 120, or (b) the feed is immediately upon entering the reactor. Or (c) the biocomponent feed can be introduced into the second or subsequent stage of the reactor containing the multi-stage hydrotreatment.

  In various embodiments, the (hydrotreated) mineral hydrocarbon feedstock 128 can be combined with the biocomponent feedstock 112 prior to entering the isomerization / dewaxing reactor 140. The mixed feedstock can be subjected to catalytic isomerization / dewaxing conditions in the presence of one or more catalyst beds containing an isomerization / dewaxing catalyst.

  The effluent 148 from the catalytic dewaxing process can optionally be hydrofinished in hydrofinishing stage 160. Depending on the equipment configuration, either effluent 148 or effluent 168 can be considered a hydroprocessing product for further use and / or processing.

Hydroprocessing Examples A series of processing runs were conducted to measure catalyst activity and products resulting from the processing of feedstock with various isomerization / dewaxing catalysts. Table 1 provides a description of four such catalysts.

  The catalysts in Table 1 were used for hydroprocessing various mixtures of mineral and biocomponent feeds. Hydrotreated diesel fuel products were used as mineral feeds for all biocomponent and mineral feed mixtures. Hydrotreated diesel fuel was mixed with either non-hydrogenated soybean oil (raw material containing triglycerides) or non-hydrogenated fatty acid methyl ester formed from rapeseed oil.

Table 2 shows a series of reaction conditions for continuous operation. Each of the catalysts 1-4 was exposed to these conditions in a separate run. For each of the following runs, the reaction pressure was about 600 psig (about 4.1 MPag). The processing gas ratio was about 2100 scf / bbl (about 350 Nm ³ / m ³ ) to about 2300 scf / bbl (about 390 Nm ³ / m ³ ) of pure (about 100%) hydrogen.

  As shown in Table 2, test conditions 4, 5, 7, 8, and 9 correspond to mixed raw materials that include both biocomponents and mineral parts. Test conditions 1, 2, 6, and 10 correspond to hydrotreated diesel fuel (mineral part only). Test condition 3 corresponds to hydrotreated vegetable oil (only the biocomponent part).

  The cloud point results for various processing operations are shown in FIG. FIG. 2 shows cloud point measurements versus days on oil for treatment runs using catalysts 1-4. In FIG. 2, numbers are used to indicate the test conditions corresponding to each treatment area. The dotted line in FIG. 2 shows the cloud point before processing for each of the raw materials. Various shapes show the results after treatment for each catalyst. As shown in FIG. 2, the diamond shape corresponds to catalyst 1, the circle corresponds to catalyst 2, the triangle corresponds to catalyst 3, and the square corresponds to catalyst 4.

Catalysts 1 and 2
FIG. 2 shows that both Catalyst 1 and Catalyst 2 provided some cloud point reduction for the deoxygenated biocomponent feed. Test condition 3 corresponds to a raw material containing only hydrogenated vegetable oil. The initial cloud point for this feed was about 20 ° C. Exposing this feed to catalyst 1 at a dewaxing temperature of about 349 ° C. resulted in a cloud point product of about 0 ° C. to about 5 ° C. A similar process using Catalyst 2 resulted in a cloud point product of about -10 ° C to -5 ° C.

Catalyst 3
Catalyst 3 was generally effective for isomerization of mineral raw materials, as shown in FIG. In Test Conditions 1 and 2, Catalyst 3 resulted in a cloud point improvement of about 20 ° C. to 40 ° C. compared to the feed, depending somewhat on the processing temperature. Catalyst 3 performed similarly for vegetable oil that had been hydrotreated in advance of Test Condition 3. Exposing the hydrotreated vegetable oil to Catalyst 3 at a higher processing temperature of about 349 ° C. resulted in a product having a cloud point of about −25 ° C. to −35 ° C. This corresponds to a cloud point drop of more than about 40 ° C. or more than about 50 ° C. compared to a raw material cloud point of about 20 ° C. This is comparable to the cloud point reduction achieved for the mineral raw material treated at about 349 ° C. in Test Condition 1.

  Applicants also note that there is some variation in the data for the various mineral raw material only conditions, corresponding to test conditions 1, 2, 6, and 10. In particular, test condition 6 occurs twice. In both cases, test condition 6 shows lower activity for catalyst 3. Furthermore, the activity against cloud point reduction in test condition 6 that occurred the second time is slightly higher than when it occurred the first time.

  Without being constrained by any particular theory regarding the cause, Applicants note that the presence of biocomponent moieties in test conditions 4, 5, 7, 8, and 9 resulted in the production of water. . Water can potentially affect catalyst activity in a few ways. One effect could be some level of catalyst poisoning due to the presence of water. It is pointed out that test condition 6 first occurred immediately after the test condition using about 50% by weight biocomponent raw material. This test condition showed minimal catalyst activity for cloud point reduction. Before test condition 6 occurred a second time, only about 20 wt% biocomponent raw material was used. Test condition 6 showed somewhat greater activity for cloud point reduction. The catalyst appeared to recover further at test condition 10, which is also a mineral source. Another effect of water could be due to catalyst degradation. This particular catalyst sample was inspected after the entire series of test conditions was completed. The bound catalyst particles appeared to break up into much smaller pieces. This may have been due to decomposition of the catalyst binder due to the presence of excess water.

Catalyst 4
Under test condition 3, catalyst 4 had only a minor effect on the cloud point of the hydrotreated vegetable oil. As shown in FIG. 2, treatment with catalyst 4 resulted in a cloud point reduction of only about 5 ° C. at both temperatures (about 332 ° C. and about 349 ° C.). Based on the results from test conditions 8 and 9, it is pointed out that it appeared to have higher activity at temperatures above about 370 ° C. Thus, the treatment at a higher temperature was able to improve the cloud point lowering activity of the catalyst 4.

  Although the present invention has been described and illustrated by reference to particular embodiments, those skilled in the art will fully appreciate that the present invention contemplates variations that are not necessarily illustrated herein. . For this reason, therefore, reference should be made solely to the appended claims for purposes of determining the true scope of the present invention.

Claims (15)

A step of mixing a bio-component raw material part with a mineral raw material part to form a mixed raw material oil,
The mixed feedstock has a sulfur content of less than about 500 wppm;
The biocomponent feed portion is at least about 25% by weight of the mixed feedstock; and the mixed feedstock is isomerized / under effective isomerization and / or dewaxing conditions comprising a temperature of at least about 350 ° C. A step of contacting with a dewaxing catalyst,
The isomerization / dewaxing catalyst comprises ZSM-48 and at least 0.5 wt% Pt, Pd, or combinations thereof;
The ZSM-48 has a silica to alumina ratio of about 75: 1 or less;
The isomerization and / or dewaxing conditions are sufficient to produce an isomerization and / or dewaxing product having a cloud point below about −20 ° C .;
A method for isomerizing and / or dewaxing diesel fuel, wherein the biocomponent feed portion is hydrotreated before contacting the mixed feedstock with an isomerization / dewaxing catalyst. Hydrotreating said feedstock under effective hydrotreating conditions comprising a biocomponent portion of at least about 25% by weight of the feedstock;
The biocomponent portion having an oxygen content of at least about 8% by weight prior to hydrotreating; and effective hydroisomerization and / or dewaxing of the hydrotreating feedstock comprising a temperature of at least about 370 ° C. Contacting with an isomerization / dewaxing catalyst under conditions comprising:
The isomerization / dewaxing catalyst comprises a molecular sieve selected from Beta, USY, ZSM-5, ZSM-35, ZSM-23, ZSM-48, or combinations thereof, wherein at least one of Ni and W and Mo At least about 2% by weight of hydrogenated metal in combination with
Diesel fuel isomerization and / or dewaxing, wherein the isomerization / dewaxing conditions comprise a step that is effective to produce an isomerization and / or dewaxing product having a cloud point below about −20 ° C. Method.   The method of claim 2, wherein the molecular sieve is ZSM-23 or ZSM-48 having a silica to alumina ratio of about 90: 1 or less.   4. The method of claim 2 or 3, wherein the dewaxing catalyst comprises at least about 2 wt% Ni and at least about 10 wt% W, Mo, or combinations thereof.   Combining the hydrotreated feedstock with a second feedstock prior to the contacting step with the isomerization / dewaxing catalyst, wherein the mixed feedstock has a sulfur content of about 100 wppm sulfur to about 500 wppm sulfur. The method in any one of Claims 2-4 further including the process which has these.   The mineral raw material portion is hydrotreated by contacting it with a hydroprocessing catalyst comprising at least one hydrogenated metal under effective hydroprocessing conditions prior to mixing with the biocomponent raw material portion. The method according to 1.   The method according to claim 1 or 6, wherein the mineral raw material portion is mixed with the biocomponent raw material portion before hydrotreating the biocomponent raw material portion.   6. The method of any of claims 2-5, wherein the second feedstock comprises a mineral feedstock portion that is hydrotreated under effective hydrotreating conditions prior to mixing with the biocomponent feedstock.   9. A process according to any one of the preceding claims, wherein the isomerization and / or dewaxing product is hydrofinished under effective hydrofinishing conditions. The effective hydroprocessing and / or hydrofinishing conditions include a temperature of about 315 ° C. to about 425 ° C., a total pressure of about 300 psig (about 2.1 MPag) to about 3000 psig (about 21 MPag), about 0.2 hr ^−1. 10. An LHSV of from about 10 hr ⁻¹ and a hydroprocessing gas ratio of from about 500 scf / bbl (about 84 Nm ³ / m ³ ) to about 10,000 scf / bbl (about 1700 Nm ³ / m ³ ). The method of crab. The step of hydrotreating the feedstock produces a hydrotreating feedstock and a gas phase effluent containing H ₂ S, and contacting the hydrotreating feedstock with the isomerization / dewaxing catalyst. 11. The method of any of claims 2-10, wherein the step further comprises contacting at least a portion of the gas phase effluent with the isomerization / dewaxing catalyst.   The method according to claim 1, wherein the biocomponent raw material part includes fat and / or oil derived from at least one of plants, animals, fish, and algae. The effective catalytic isomerization / dewaxing conditions include about 400 psig (about 2.8 MPag) to about 1500 psig (about 10.3 MPag) total pressure, about 0.5 hr ⁻¹ to about 5.0 hr ⁻¹ LHSV, And a process gas ratio of from about 500 scf / bbl (about 84 Nm ³ / m ³ ) to about 2000 scf / bbl (about 340 Nm ³ / m ³ ).   14. A method according to any one of the preceding claims, wherein the hydrotreating feed stream is transferred to the isomerization / dewaxing step without intermediate separation.   (I) the mixed feedstock has a sulfur content of about 50 wppm or less and a nitrogen content of about 20 wppm or less, or (ii) the hydrotreated feedstock has a sulfur content of about 100 wppm sulfur to about 500 wppm sulfur. Or (iii) (i) and (ii) both.

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